Carbonato esters of fatty acids



2,826,591 CARBONATO ESTERS F FATTY ACIDS -William L. Rierleman, Philadelphia, Pa.,"assignor"to Rolim 85 Haas Company,lhiladelphia, Pa., a-corporation of Delaware NoDrawing. Application April 21, 1954 Serial No. 424,758

14 Claims. (CL 260'-340.2)

formula in each acid portion of the esters.

containing one to 14 carbon atoms. --preparat1on and use of the carbonato esters.

esters which do not contain carbonato groups. -1ngly, they are recommended for use as plasticizers in V More particularly it relates to carbonatostearates having the formula in which R represents a monovalent hydrocarbon radical It also relates to the The compounds of this invention are unusually high boiling liquids which have lubricating properties in their own right and are highly compatible with a wide variety of plastic materials. By virtue of the presence of the carbonato groups in the fatty acid chains, they are far more compatible with plastic materials, such as cellulosic esters and vinyl halide resins, than are the corresponding Accordplastic compositions.

saturated acid which The products of this invention can be made by at least two methods. In one process, phosgene is reacted with an ester containing at least two hydroxyl groups on adjacent carbon atoms of the acid moiety of the ester. Hydrogen chloride is split out and, therefore, the reaction is best carried out in the presence of an acceptor for hydrogen chloride. In another process, the same kind ofpolyhydroxylated ester is reacted with a dialkylcarbonate, such as dimethyl carbonate or diethyl carbonate, by ester-interchange in the presence of a catalyst such as metallic sodium or an alkali metal alkoxide.

- In either process, the starting material is an ester which contains one or more pairs of hydroxyl groups on ad- -jacent carbon atoms portion of the ester.

of the aliphatic chain in the acid Such polyhydroxyl esters are made For example, an ester of an uncontains one or more double bonds by known methods.

is "reacted with hydrogen peroxide and a large excess of "p'olyhydroxy compound 1 "group, or by alcoholysis according to the formic acid or acetic acid whereby an hydroxy-acyloxy This, in turn, is converted to the by hydrolysis of the acyloxy process of U. S.

derivative is produced.

Patent No. 2,669,572.

It is now evident that the starting material is an 'ester of an acid which contains 16 to 22 carbon atoms and which also contains one or more double bonds. Typical of such acids are oleic acid, ClllClC'flCld, elaeo- "stearic acid, linoleic acid, linolenic acid, clupanodonic Unite States Patent ice - acid, palmitoleic acidand palmitolenic acid. All of these acids occurin animal or vegetable oils, for example, in soybean, rapeseed, linseed, sardine and whale oils and are readily obtained by the saponification of the -naturally occurring oils. The esters of the fatty acids which are converted by the process of this invention tobarbonato esters are those of monohydric and polyhydric alcohols typified bythe following: mono-, di-, and

-tri-substituted carbinols, such as ethyl, isopropyl, nbntyl, sec-butyl, tert-butyl, tert-amyl, n-octyl, Z-ethylhexyl, octadecyl, lauryl, cyclohexyl and benzyl; polyhydric alcohols, such as ethylene glycol, 1,2-propylene glycol, Z-ethylhexandiol-LB, butandiol-1,2, butandiol-l,3, butandiol-l,4,

dodecandiol-l,l2, polyalkylene glycols, such as diethylene glycol; glycerol; pentae'rythritol; and the isomers and homologues of the above. This invention also embraces mixed esters such as ethylene oleate-linoleate, glyceryl di-oleate-monolinoleate, butylene linoleate-oleate, and the a like. The naturally occurring vegetable and. animal oils likewise give rise to the carbonato esters of this invention. These oils are mixed esters of glycerol and a mixture of the acids mentioned above, and include the following: soybean, corn, cottonseed, safflower, sunflower, sesame, poppyseed, walnut, peanut, linseed, sardine, perilla and fish oils in general. Since all of these esters contain aliphatic unsaturation, they can readily be converted first tothe polyhydroxy derivative and thereafter to the carbonato products. While it is preferred that all of the double bonds in any given ester be converted to carbonato groups, complete conversion is sometimes difiicult to obtain, especially in the case of the naturally occurringoils. It has been found, however, that the carbonato groups impart to esters the greatly enhanced solubility in, and compatibility with, plastic materials, particularly nitrocellulose, cellulose esters or resins of the vinyl halide type. Therefore, it is not essential that every double bond be converted to a earbonato group. It is essential, however, that at least one double bond in each acid chain be thus converted on the average. In the case of the esters of the polyhydric alcohols-particularly the naturally occurring oils which are esters of glycerol and a mixture of acids, including saturated and unsaturated acids-it is essential that at least one carbonato group be present for each acid moiety of said ester. Thus, when the glyceride oils are considered, it is necessary to have present an average of at least three carbonato groups per molecule of glyceride oil. It is virtually impossible to direct the reaction so that the carbonato groups are distributed uniformly in every acid chain; but for practical purposes. the introduction of an average of at least one carbonato group for each acid moiety is required so that the resultant ester will have satisfactory compatibility with plastic materials.

have proven to be especial- The carbonato esters which 'ly valuable as plasticizers for vinyl resins and which,

therefore, have the greatest commercial promise at the t moment are those of 9,10-carbonatostearic acid having the general formula practice, it is preferred to carry out the reaction at?) temperature from about C. to about 60 C. because of the volatility of the phosgene. The phosgene may be bubbled into the ester; but a more satisfactory method appears to be that of reacting the ester with a solution of phosgene in an organic liquid, such as benzene, which is a solvent for the hydroxylated ester. It is most desirable that a mildly basic acceptor for hydrogen chloride be present; and for this purpose tertiary amines and weakly basic anion-exchange resins have each been used. Pyridine is very effective and its use is recommended at lower temperatures while anion-exchange resins are best used at higher temperatures. Other tertiary amines which can be used like pyridine include quinoline, isoquinoline, dimethylaniline, diethylaniline, trimethylamine, triethylamine, trim-butylamine, and the like. What is desired is that an acceptor be present which will take up the hydrogen chloride as fast as it is formed without causing saponification of the ester. In the process of preparing the carbonate esters by ester-interchange, the ester is reacted with an alkyl carbonate at a temperature which is high enough to cause the alcohol to distill out of the reaction mixture. Here, as in the phosgene reaction, the use of a solvent, such as an aromatic hydrocarbon, is recommended; or an excess of the alkyl carbonate itself may serve as a solvent. Alkali metals, such as sodium and potassium, serve as excellent catalysts. Metal alkoxides have also been used.

The property which makes the products of this invention so efiicient as plasticizers, particularly for vinyl halide resins, is their stability in plastic compositions. They are readily dispersed in plastic compositions and therea ter remain permanently in the compositions. They are not easily extracted by means of solvents or aqueous solutions and they do not tend to migrate to the surfaces of such compositions. At the same time, they impart a high degree of flexibility which is retained even at low temperatures. The vinyl resins which can be plasticized to advantage with the carbonate esters of this invention are more properly defined as vinyl halide resins and this term is herein used to embrace the following: Polymers of a vinyl halide, such as vinyl chloride and vinyl bromide; copolymers of a vinyl halide and a vinyl ester of the lower aliphatic acid, such as copolymers of vinyl chloride and vinyl acetate or vinyl propionate; copolymers of vinyl halides, such as vinyl chloride, and vinylidene halides, such as vinylidene chloride; and co-polymers of a vinyl halide with other copolymerizable compounds containing a vinylidene group, CH2=C such as ethyl acrylate, methyl methacrylate and the like. Preferred copolymers of this type are those which contain from about 60 to about 95% of copolymerized vinyl chloride and 5% to 40% of the other copolymerized vinylidene compound.

The following examples are intended to illustrate the manner in which the compounds of this invention may be made and utilized. The examples are drawn to the preparation and use of esters of 9,10-carbonatostearic acid; but it is to be understood that the other esters embraced by this invention are prepared in the same manner and are employed in the same way in plastic compositions.

Example 1 Into a reaction vessel equipped with an agitator, thermometer and gas-inlet tube there was charged 125 grams of a mixture of the lauryl ester and the myristyl ester of 9,10-dihydroxystearic acid dissolved in 250 ml. of henzene. To this was added 110 grams of a weakly basic anion-exchange resin containing tertiary amine groups. In a separate container was prepared a solution of 37 grams of phosgene dissolved in 150 grams of benzene. The solution of the ester was stirred and to it was added slowly over a period of minutes the benzene solution of phosgene. The latter was added at such a rate that the temperature was maintained between 40 and since the reaction is exothermic. Thereafter the reaction mixture was held at 40 to 45 for a period of 2 /2 hours and was then filtered to remove the particles of anionexchange resin. The filtrate was then stripped under vacuum to remove benzene and other volatile constituents. The oil residue was thereafter purified by molecular distillation and gave rise to an essentially colorless oil which, by analysis, was shown to contain essentially the theoretical number of carbonato groups.

In the same manner the individual n-octyl and Z-ethylhexyl esters of carbonatostearic acid were prepared. Also a mixture of the decyl and lauryl esters of carbonatestearic acid was prepared in the same way by the reaction of phosgene with a mixture of decyl and lauryl dihydroxystearates. All of the products were high boiling oils which were compatible with polyvinyl chloride and with a copolymer of vinyl chloride and vinylidene chloride.

Example 2 To a three-necked reactor equipped with a mechanical agitator, thermometer, condenser, and water-separator was charged grams of n-hexyl 9,10-dihydroxystearate, 32.5 grams of diethyl carbonate and approximately 0.25 gram of metallic sodium. The stirred reaction mixture was heated to C. Ethyl alcohol which was liberated from the reaction mixture was collected in the water separator. Over a period of six hours the temperature of the reaction mixture rose gradually to C. during which time a total of 19 grams of liquid condensed and was collected in the separator. The reaction mixture was then carefully stripped under vacuum to remove residual volatile constituents. The oily residue was dissolved in 100 grams of benzene and the solution was washed with a 2% aqueous solution of oxalic acid until the basicity was neutralized and was thereafter thoroughly washed to neutrality with water. The benzene solution was then dried over anhydrous magnesium sulfate and was filtered. The benzene was removed under vacuum and a product was obtained which was subsequently purified by molecular distillation yielding 61 grams of an essentially colorless oil whose analysis corresponded to that of hexyl 9,10-carbonatostearate.

. Example 3 The general procedure of Example 1 Was followed. Here, however, pyridine was used as the HCl-acceptor in place of the anion-exchange resin used in the first example. Thus 100 grams of 2-ethylbutyl dihydroxystearate (0.5 mol) was dissolved in 55.3 grams of pyridine and was reacted with a solution of 29.7 grams of phosgene (0.3 mol) dissolved in 100 grams of toluene. The reaction mixture was maintained at a temperature of -5 to 0 C. while the phosgene solution was added (35 min.). The reaction mixture was held first at 0 to 2 C. for 2 hours and then at about 20 C. for 2 hours. Thereafter the reaction mixture was washed thoroughly, stripped of benzene and pyridine and was purified by distillation (boiling range 240 C./ 1.3 mm. to 263 C./ 0.4 mm.). The prod uct, 2-ethylbutyl carbonatostearate, was a pale oil having an index of refraction (n of 1.4573. Its composition was confirmed by analysis (percent C: theory=70.39, analysis=70.47; percent H: theory=10.82, analysis: 10.92).

In a similar manner the Z-ethylhexyl ester of carbonatostearic acid was prepared. It was essentially identical with the 2-ethylhexyl carbonatostearate prepared'by the process of Example 1.

By the same method the n-butyl ester of carbonatostearic acid was prepared. It, too, was a pale oil whose composition was confirmed by analysis (percent C: theory=69.3l, analysis=69.27; percent H: theory: 10.62, analysis=10.54; ;1 =l.4560; boiling range: 247-254 C./O.6 mm).

Also by the same method the fi-chloroethyl ester of carbonoste'aric acid was prepared. Its index ofrefraction Example 4 Into a reaction vessel equipped with a stirrer, thermometer, reflux condenser and dropping funnel was charged a solution of 163 grams (0.4 mol) of benzyl 9,10-dihydroxystearate in 200 ml. of toluene. Next there was added 79 grams of pyridine. The stirred solution was cooled and was maintained at a temperature of 0.-5 C. while a solution of 60 grams (0.6 mol) of phosgene in 200 m1. of toluene (cooled to -5 C.) was added over a period of about one-half hour. The reaction mixture was stirred at 0-5 C. for an hour, after which it was allowed to warm up to room temperature and was held at room temperature for 16 hours. Then the reaction mixture was transferred to a separatory funnel and was shaken with 100 ml. of water and then with three 500 ml.- portions of water, 100 ml. of a 2% aqueous solution of sodium carbonate and again with two 500 mL-portions of water. The organic phase was stripped free of toluene under vacuum. The crude product was purified by distillation in a short path still. The product, benzyl 9,10- carbonatostearate, was an oil which boiled at 255-270 C./0.20 mm., and which had an index of refraction of n =l.5390. its composition was confirmed by analysis (percent C: theory=72.20, analysis=72.50; percent H: theory=9.34, analysis=9.45). Like the products of the previous examples, it was compatible with polyvinyl chloride and with a copolymer of about 95% vinyl chloride and about 5% vinyl acetate, and exercized a real plasticizing action.

Example 5 In essentially the same manner as described in Example 4, a carbonatostearate was made from the Z-ethylbutyl ester of tetrahydroxy stearic acid (which had been made from linoleic acid). One-half mol (198 grams) of 2- ethylhexyl tetrahydroxystearate was fused and dissolved in 200 m1. of toluene and the solution was charged to the reaction vessel together with 240 grams of pyridine and cooled to 05 C. It was maintained within that temperature range while a solution of 140 grams (1.4 mols) of phosgene in 200 ml. of toluene was slowly added. When of the phosgene solution had been added, 200 ml. of toluene was also added and an acetone-Dry Ice bath was employed to maintain the temperature within the range of 0-5 C. The remainder of the phosgene solution was added, followed by a one-hour period of stirring at 0-5 C. and 16 hours at room temperature. The product was worked up and isolated in the manner described above. It was a viscous oil. Analysis of the carbonato ester showed that it contained an average of more than one carbonato group per molecule of ester but not quite two carbonato groups. It was, however, compatible with polyvinyl chloride. A solution of polyvinyl chloride and 40% of the carbonato ester (on a dry basis) dried to a clear, tough, tack-free film which was much softer than a film of the polyvinyl chloride alone. See continuation-in-part application Serial No. 474,269 filed December 9, 1954.

I claim:

1. A carbonato vegetable oil which contains, in acid moieties of said oil, a group of the formula 2. A carbonato ester of a fatty acid derived from natural fats and oils, which contains in the alcohol moiety thereof one to 18 carbon atoms free of non-aromatic unsaturation, and which contains in an acid moiety thereof a group of the formula and 16 to 22 carbon atoms excluding carbonato carbon atoms.

3. Carbonato soybean oil which contains a carbonato group per acid moiety of said oil.

4. Carbonato safiiower oil which contains a carbonato group per acid moiety of said oil.

5. A carbonato ester which has the general formula in which R is a monovalent hydrocarbon group free of non-aromatic unsaturation and containing one to 14 carbon atoms.

6. Octyl 9,10-carbonatostearate.

7. Decyl 9,10-carbonatostearate.

8. Lauryl 9,10-carbonatostearate.

9. A process for preparing carbonato esters which comprises reacting, in substantially equivalent amounts and in the presence of a mildly basic hydrogen chloride acceptor, phosgene and an ester of a fatty acid derived from natural fats and oils which contains in the alcohol moiety thereof one to 18 carbon atoms free of non-aromatic unsaturation and which contains in an acid moiety thereof 16 to 22 carbon atoms and which also contains on said acid moiety at least one pair of hydroxyl groups on adjacent carbon atoms.

10. A process for preparing carbonato esters which comprises reacting, in substantially equivalent amounts and in the presence of a mildly basic hydrogen chloride acceptor, phosgene and an ester of 9,10-dihydroxystearic acid, which ester contains one to 18 carbon atoms free of non-aromatic unsaturation in the alcohol moiety thereof.

11. A process for preparing carbonato esters which comprises reacting, in substantially equivalent amounts and in the presence of a mildly basic hydrogen chloride acceptor, phosgene and an octyl ester of 9,10-dihydroxystearic acid.

12. A process for preparing carbonato esters of glycerol which comprises reacting, in substantially equivalent amounts and in the presence of a mildly basic hydrogen chloride acceptor, phosgene and a glyceryl ester of a fatty acid derived from natural fats and oils which contains 16 to 22 carbon atoms and which also contains at least one pair of hydroxyl groups on adjacent carbon atoms of the acid moiety.

13. A process for preparing carbonato esters which comprises reacting, in substantially equivalent amounts and in the presence of a mildly basic hydrogen chloride acceptor, phosgene and a decyl ester of 9,10-dihydroxystearic acid.

14. A process for preparing carbonato esters which comprises reacting, in substantially equivalent amounts and in the presence of a mildly basic hydrogen chloride acceptor, phosgene and a lauryl ester of 9,10-dihydroxystearic acid.

References Cited in the file of this patent UNITED STATES PATENTS 1,995,291 Carothers Mar. 26, 1935 2,379,261 Strain June 26, 1945 2,397,630 Strain Apr. 2, 1946 2,446,145 Strain July 27, 1948 2,595,310 Smith May 6, 1952 2,664,410 Darby et a1. Dec. 29, 1953 

2. A CARBONATO ESTER OF A FATTY ACID DERIVED FROM NATURAL FATS AND OILS, WHICH CONTAINS IN THE ALCOHOL MOIETY THEREOF ONE TO 18 CARBON ATOMS FREE OF NON-AROMATIC UNSATURATION, AND WHICH CONTAINS IN AN ACID MOIETY THEREOF A GROUP OF THE FORMULA 